CN108410266A - A kind of novel invisible anti-fake two-dimension code based on nano metal organic framework materials - Google Patents
A kind of novel invisible anti-fake two-dimension code based on nano metal organic framework materials Download PDFInfo
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- CN108410266A CN108410266A CN201810193083.9A CN201810193083A CN108410266A CN 108410266 A CN108410266 A CN 108410266A CN 201810193083 A CN201810193083 A CN 201810193083A CN 108410266 A CN108410266 A CN 108410266A
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/50—Sympathetic, colour changing or similar inks
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G83/00—Macromolecular compounds not provided for in groups C08G2/00 - C08G81/00
- C08G83/008—Supramolecular polymers
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/30—Inkjet printing inks
- C09D11/36—Inkjet printing inks based on non-aqueous solvents
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- G—PHYSICS
- G06—COMPUTING; CALCULATING OR COUNTING
- G06K—GRAPHICAL DATA READING; PRESENTATION OF DATA; RECORD CARRIERS; HANDLING RECORD CARRIERS
- G06K19/00—Record carriers for use with machines and with at least a part designed to carry digital markings
- G06K19/06—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code
- G06K19/06009—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code with optically detectable marking
- G06K19/06037—Record carriers for use with machines and with at least a part designed to carry digital markings characterised by the kind of the digital marking, e.g. shape, nature, code with optically detectable marking multi-dimensional coding
Abstract
A kind of novel invisible anti-fake two-dimension code based on nano metal organic framework materials.The novel invisible anti-fake two-dimension code is made of nano metal organic framework materials ink printed at adjustable with quantity, equal-sized hidden code block and three Black vertices positioning squares, to encode fluorescence color of the square under specific wavelength excitation as information memory cell.The fluorescence color of coding square carries coding information, and almost infinite more fluorescence color can be obtained by being mixed three primary colours fluorescent emission ink by ink-jet printer, to realize infinite more coding information.Moreover, the also size of coding information capacity can be realized by adjusting the quantity of cell encoding square.To realize this novel invisible anti-fake two-dimension code, it is desirable that prepare the nanoscale invisible ink of three primary colours fluorescent emission；Meanwhile three primary colours and its mixing chromatic ink not display color in the sunlight, the fluorescence of different colours is emitted under the excitation of single wavelength light.
Description
Technical field
The invention belongs to inkjet printing concealed anti-false Quick Response Code application fields, more particularly to a kind of fluorescence color that is based on is information
The anti-fake code of storage content.Content is related to the preparation of the three primary colours fluorescent emission ink under single excitation, according to three primary colours original
Reason realizes that full-color inkjet prints concealed fluorescent anti-fake two-dimension code.
Background technology
Fraud problem, which has become, threatens businessman, enterprise, government, the finance even global problem of human health.Therefore,
There is an urgent need to the anti-counterfeiting technologies for developing some hardly possible duplications, easily authorizing to protect important file, luxury goods, currency, drug, certificate
Deng.In recent years, the Quick Response Code based on photoetching, laser engraving, silk-screen printing and inkjet printing be applied to label and it is anti-fake.
Wherein, inkjet printing technology due to its designability is strong, low cost, high yield, the remarkable advantages such as simple for production and extensive use.
Quick Response Code be it is a kind of using certain specific geometric figure be distributed according to certain rules in plane (on two-dimensional directional) it is chequered with black and white
Graphic recording data symbol information, have the characteristics that information capacity is big, reliability is high, be easy to make, is at low cost, to
It is widely used.At the same time, due to the transreplication of existing visual Quick Response Code and be easy by offender load wooden horse disease
The safety of the shortcomings of malicious, Quick Response Code are faced with huge challenge.Therefore, development ciphering type Quick Response Code is urgently to be resolved hurrily at present
Problem.To solve this problem, currently reported by modifying fluorescent organic dyes, quantum dot, up-conversion nanoparticles etc.
Method carries out two-dimentional code encryption.
Currently, fluorescence falsification preventing Quick Response Code has following several types：Rare earth metal up-conversion nanoparticles, this kind of luminescent material
Fluorescence is adjustable, high resolution and photostability is strong, e.g., 1) Meruga, J.M., Baride, A., Cross, W., Kellar,
J.J.&May,P.S.Red-green-blue printing using luminescence-upconversion
Inks.Journal of Materials Chemistry C 2014,2,2221. but such luminescent material synthetic method complexity
And be difficult to overcome, while needing daily long wavelength laser difficult to use；It is prepared by carbon dots or quantum dot or fluorescent organic dyes
Simply, e.g., 2) Jiang, K.et al.Triple-Mode Emission of Carbon Dots:Applications for
Advanced Anti-Counterfeiting.Angewandte Chemie 2016,55,7231-7235；3)Hou,X. et
al.Tunable solid-state fluorescent materials for supramolecular
encryption.Nature Communications 2015,6,6884；4)Kumar,P.,Singh, S.&Gupta,
B.K.Future prospects of luminescent nanomaterial based security inks:from
synthesis to anti-counterfeiting applications. Nanoscale 2016,8,14297-14340。
But such material emission wavelength has limitation and photobleaching easily occurs.Above-mentioned material synthesis complexity, complex steps, limit it
Application in inkjet printing anti-fake two-dimension code.Therefore, exploitation synthesis is simple, luminous intensity is high, photostability is strong, excitation wave
The long nano-luminescent material being easy to get for inkjet printing anti-fake two-dimension code there is important learning value and practical application to anticipate
Justice.
The present invention is directed to develop, a kind of anti-fake degree is high, novel invisible anti-fake two-dimension code easy to operate.Using synthesis letter
Single, versatile red, green, blue three primary colours fluorescence nano metal-organic framework material is as ink raw material, with fluorescence color
As signal memory cell, information storage is realized by the design and arrangement of storage unit encoding block fluorescence color, by ultraviolet
2 D code information extraction is realized in the excitation of lamp single wavelength.Fluorescence concealed anti-false Quick Response Code proposed by the present invention takes full advantage of nanometer
Suitable dimension, three primary colours fluorescent emission and the single excitation wavelength characteristic of metal-organic framework material, are realized by inkjet printing
The multiple anti-fake function of novel invisible Quick Response Code.
Invention content
The present invention, there are problem, is proposed using fluorescence color as the novel encryption anti-counterfeiting of signal identification unit two dimension for above-mentioned
Code.The New Two Dimensional code is made of the adjustable hidden code block of equal in magnitude, quantity and three Black vertices locating pieces, each
The color of hidden code block fluorescence carries a coding information.The novel encryption anti-counterfeiting Quick Response Code only shows that black is fixed in the sunlight
Position block realizes information decryption under the ultraviolet excitation of specific wavelength, shows coding information identical with input information.Design is closed
At the three primary colours concealed fluorescent nanometer MOFs of single excitation, and it is modified the three primary colours ink for being prepared into suitable inkjet printing
Water, and develop the multiple application of its concealed anti-false Quick Response Code or individualized security.
Technical scheme of the present invention：
Using fluorescence color as the novel encryption anti-counterfeiting Quick Response Code of signal identification unit.The New Two Dimensional code by it is equal in magnitude,
The adjustable hidden code block of quantity and three Black vertices locating piece compositions, the color carrying one of each hidden code block fluorescence
A coding information.Black locating piece is only shown in the sunlight, and information decryption, display are realized under the ultraviolet excitation of specific wavelength
Coding information identical with input information.
The novel encryption anti-counterfeiting Quick Response Code is a kind of novel invisible based on nano metal organic framework materials fluorescent ink
Anti-fake two-dimension code.The preparation process of ink is as follows：
1) by anhydrous group of the lanthanides chloride, 1,3- terephthalic acid (TPA), 3,5- dicarboxyl phenyl boric acids are added to N, N- dimethyl methyls
In amide and water, ultrasonic dissolution 10min obtains homogeneous transparent mixed liquor；
2) mixed liquor is added in polytetrafluoroethylliner liner and is inserted in reaction kettle, be put into baking oven, heated at 120 DEG C
Reaction 6 hours, obtains reaction solution, has white precipitate precipitation in bottom；
3) precipitation is centrifuged with supernatant, respectively washing 2 times of n,N-Dimethylformamide and ethyl alcohol is used in combination, finally do
It is dry to can be obtained nano metal organic framework material Ln-NMOFs；
The anhydrous group of the lanthanides chloride is Europium chloride in one of the embodiments, obtains Eu-NMOFs,
Red fluorescence is shown under the laser irradiation of 275nm wavelength；
The anhydrous group of the lanthanides chloride is terbium chloride in one of the embodiments, obtains Tb-NMOFs,
Green fluorescence is shown under the laser irradiation of 275nm wavelength；
The anhydrous group of the lanthanides chloride is dysprosium chloride in one of the embodiments, obtains Dy-NMOFs,
Blue-fluorescence is shown under the laser irradiation of 275nm wavelength；
The anhydrous group of the lanthanides chloride, 1,3- terephthalic acid (TPA)s, 3,5- dicarboxyls phenyl boric acid and N,N-dimethylformamide,
The amount ratio of water is 0.02mmol:0.01mmol:0.01mmol:7mL:3mL.
Uio-66-NH2Synthesis it is as follows：
1) 77mg zirconium chlorides, 48mg amino terephthalic acid (TPA) and 600mg benzoic acid are added to 6mL N, N- dimethyl methyls
In amide and 55L HCl, ultrasonic dissolution 10min obtains homogeneous transparent mixed liquor；
2) mixed liquor is added in the reaction kettle of 30mL polytetrafluoroethylliner liners, is put into baking oven, reaction is heated at 120 DEG C
24 hours, obtaining to bottom had the reaction solution that white precipitate is precipitated；
3) it will precipitate after being centrifuged with supernatant, with n,N-Dimethylformamide and ethyl alcohol respectively washing 2 times, finally freeze
It is dry, obtain the nano metal organic framework material Uio-66-NH for emitting stronger blue-fluorescence2；
The modification preparation process of concealed fluorescent ink is as follows：
A ultrasonic disperse 15min in ethyl alcohol) is added in dry fluorescence NMOFs materials, and 0.5h is stirred at room temperature.
B ink solvent) is added, including:Ethylene glycol, glycerine, diethylene glycol (DEG) and surfactant SDS are ultrasonic again
15min, and room temperature quickly stirs 2h.
In one of the embodiments, in step A) in, Eu-NMOFs powder is 20mg, and ethyl alcohol is 450 L；In step B)
In, ethylene glycol 450L, glycerine 50L, diethylene glycol (DEG) 50L, surfactant SDS (3mg/mL) is 500L.
In one of the embodiments, in step A) in, Tb-NMOFs powder is 10mg, and ethyl alcohol is 450 L；In step B)
In, ethylene glycol 450L, glycerine 50L, diethylene glycol (DEG) 50L, surfactant SDS (3mg/mL) is 500L.
In one of the embodiments, in step A) in, Uio-66-NH2Powder is 30mg, and ethyl alcohol is 450 L；In step
B in), ethylene glycol 450L, glycerine 50L, diethylene glycol (DEG) 50L, surfactant SDS (3mg/mL) is 500L.
The three primary colours fluorescent emission ink synthesized above is filling in the print cartridge of ink-jet printer respectively, by default colour
Anti-fake two-dimension code is printed to A4 paper, print procedure smoothness out of ink, no to block, and A4 paper is placed in the ultraviolet of 275nm wavelength
Under light source, it is seen that clearly color fluorescence Quick Response Code, imaging are accurate.
The nano metal organic framework material of synthesis emits red, green, blue three primary colours fluorescence respectively, by three kinds of materials into
Row modification is prepared into the three primary colours fluorescent ink that can be used for inkjet printing.It proposes using fluorescence color as the novel of signal identification unit
Anti-fake two-dimension code, a fluorescence color correspond to a coding information, are mixed and printed by three primary colours, can obtain abundant storage
Information realizes antiforge function, since ink color has the function of concealed anti-false close to colourless under daylight.In addition, by setting
The quantity for counting colored information unit block in Quick Response Code, is adjusted the information capacity of Quick Response Code.
It is an advantage of the invention that：Using fluorescence color as signal identification unit, realize that two-dimentional code position and the multiple of information are prevented
Pseudo- function, and such concealed anti-false ink is prepared using one pot of solvent-thermal method, it is simple for process, of low cost, easy to implement.More than
Only several embodiments of the present invention are expressed for the embodiment, the description thereof is more specific and detailed, cannot therefore be interpreted as
Limitation to the scope of the claims of the present invention.It is any that concealed anti-false is realized with three primary colours fluorescent ink under the premise of present inventive concept
The coding mode of Quick Response Code belongs to the scope of the present invention.
Description of the drawings
Fig. 1 is the design diagram of novel invisible anti-fake two-dimension code, wherein：A is that transmitting red, green, blue three primary colours are glimmering respectively
The preparation process schematic diagram of the nanometer MOFs inks of light；B is ink-jet printer cartridge retrofit process schematic diagram；C is print procedure
Schematic diagram；D is printing false-proof information encryption and decryption processes schematic diagram.
Fig. 2 is the scanning electron microscope (SEM) photograph of the host material group of the lanthanides nanometer MOFs of three primary colours ink, wherein：A is that transmitting is red glimmering
Light Eu-NMOFs；B is transmitting green fluorescence Tb-NMOFs；C is transmitting blue-fluorescence Dy-NMOFs；Illustration is corresponding transmission
Electron microscope.
Fig. 3 is the luminosity of three primary colours ink host material, wherein：A is that transmitting red fluorescence Eu-NMOFs exists
Fluorescent emission figure under the excitation of 275nm wavelength；B is the fluorescent emission for emitting green fluorescence Tb-NMOFs under 275nm excitations
Figure；C is the fluorescent emission figure for emitting blue-fluorescence Dy-NMOFs under 275nm excitations；D is the transmitting light face of three kinds of fluorescence MOFs
Position of the color in CIE.
Fig. 4 is that three primary colours ink Eu-NMOFs, Tb-NMOFs and Dy-NMOFs press 1 respectively two-by-two:0,1:2, 1:1,2:1,
0:The luminescent spectrum and the coordinate position figure in CIE obtained after 1 mixing, wherein：A be red fluorescence ink Eu-NMOFs with it is green
The mixed luminescent spectrum figures of color fluorescent ink Tb-NMOFs；B is red fluorescence ink Eu-NMOFs and blue-fluorescence ink Dy-
The mixed luminescent spectrum figures of NMOFs；C is that green fluorescence ink Tb-NMOFs and blue-fluorescence ink Dy-NMOFs is mixed
Luminescent spectrum figure；D is coordinate diagram of the mixed luminescence spectrum in CIE.
Fig. 5 is three primary colours ink Eu-NMOFs, Tb-NMOFs and Uio-66-NH21 is pressed two-by-two:0,1:2,1:1, 2:1,0:
The luminescent spectrum and the coordinate position figure in CIE obtained after 1 mixing, wherein：A is red fluorescence ink Eu-NMOFs and green
The mixed luminescent spectrum figures of fluorescent ink Tb-NMOFs；B is red fluorescence ink Eu-NMOFs and blue-fluorescence ink Dy-
The mixed luminescent spectrum figures of NMOFs；C is that green fluorescence ink Tb-NMOFs and blue-fluorescence ink Dy-NMOFs is mixed
Luminescent spectrum figure；D is coordinate diagram of the mixed luminescence spectrum in CIE.
Fig. 6 is that red fluorescence ink Eu-NMOFs and green fluorescence ink Tb-NMOFs presses 1 respectively:0,0:1, 1:1,1:
1.001,1:1.01,1:1.1,1:2,1:1.3,1:1.4 and 1:The luminescent spectrum and CIE coordinate positions obtained after 1.5 mixing.
Table 1 is that red fluorescence ink Eu-NMOFs and green fluorescence ink Tb-NMOFs presses 1 respectively:0,0:1, 1:1,1:
1.001,1:1.01,1:1.1,1:2,1:1.3,1:1.4 and 1:Coordinate position of the 1.5 mixed luminescence spectrum in CIE.
Fig. 7 is the writing effect figure of the pen core made of three primary colours ink, wherein：A, B is respectively by Eu-NMOFs, Tb-
NMOFs and Uio-66-NH2Ink is mounted in the photo of manufactured water-color paintbrush under fluorescent light and in the UV lamp in pen core；C, D is point
It Yong not red fluorescence ink Eu-NMOFs, green fluorescence ink Tb-NMOFs, blue-fluorescence ink Uio-66-NH2It writes
The acronym " N " of " Nankai University ", " K ", " U " respectively under fluorescent light with the photo under ultraviolet lamp；E is C
Surface topography in figure at box under a scanning electron microscope, the particle of high-visible uniformly complete nanometer MOFs.
Fig. 8 A-C be design input two-dimension code pattern, the Quick Response Code of printing under fluorescent light and 275nm ultraviolet lamp
Under photo；Fig. 8 D be design with fluorescence color and position be identify bar shaped bar code fluorescent lamp and ultraviolet lamp excitation under
Information.Fig. 8 E are that the heart of design is printed upon on RMB the letter under fluorescent lamp and ultraviolet lamp respectively with crescent moon superposed graph
Breath.
Specific implementation mode
Embodiment：
Transmitting is red, green, blue-fluorescence nano metal organic framework materials preparation, and be modified be prepared into it is suitable
The three primary colours ink of inkjet printing, for using fluorescence color as the New Two Dimensional code anti-counterfeiting technology of signal identification unit.
The New Two Dimensional code is the novel encryption anti-counterfeiting Quick Response Code using fluorescence color as signal identification unit, by size phase
Deng, the adjustable hidden code block of quantity and three Black vertices locating pieces compositions.The color of each hidden code block fluorescence is held
Carry a coding information.The novel encryption anti-counterfeiting Quick Response Code only shows black locating piece in the sunlight, in the ultraviolet of specific wavelength
Light excitation is lower to realize information decryption, shows coding information identical with input information.
The novel encryption anti-counterfeiting Quick Response Code is a kind of novel invisible based on nano metal organic framework materials fluorescent ink
Anti-fake two-dimension code.Nano metal organic framework materials are prepared using hydro-thermal method, and steps are as follows：
1) by 0.02mmol group of the lanthanides chlorides (EuCl3, TbCl3And DyCl3), 0.01mmol 1,3- terephthalic acid (TPA)s,
0.01mmol 3,5- dicarboxyl phenyl boric acid are added to 7mLN, and in dinethylformamide and 3mL water, ultrasonic dissolution 10min is obtained
To homogeneous transparent mixed liquor；
2) mixed liquor is added in the reaction kettle of 30mL polytetrafluoroethylliner liners, is put into baking oven, reaction is heated at 120 DEG C
6 hours, obtaining to bottom had the reaction solution that white precipitate is precipitated；
3) it will precipitate after being centrifuged with supernatant, with n,N-Dimethylformamide and ethyl alcohol respectively washing 2 times, finally freeze
It is dry, emitted the nano metal organic framework material Ln-NMOFs of red, green, blue fluorescence respectively；
The anhydrous group of the lanthanides chloride is Europium chloride in one of the embodiments, obtains Eu-NMOFs 1,
Red fluorescence is shown under the laser irradiation of 275nm wavelength；
The anhydrous group of the lanthanides chloride is terbium chloride in one of the embodiments, obtains Tb-NMOFs 2,
Green fluorescence is shown under the laser irradiation of 275nm wavelength；
The anhydrous group of the lanthanides chloride is dysprosium chloride in one of the embodiments, obtains Dy-NMOFs 3；Its
Blue-fluorescence is shown under the laser irradiation of 275nm wavelength；
In order to further verify the versatility of three primary colours fluorescent ink and improve luminosity, experiment has synthesized transmitting blue
The nanometer Uio-66-NH of fluorescence2, respectively object has been carried out with red fluorescence ink Eu-NMOFs, green fluorescence ink Tb-NMOFs
Reason mixing, verifies it and is used for the potentiality of inkjet printing；
Uio-66-NH2Synthesis it is as follows：
1) 77mg zirconium chlorides, 48mg amino terephthalic acid (TPA) and 600mg benzoic acid are added to 6mL N, N- dimethyl methyls
In amide and 55 μ L HCl, ultrasonic dissolution 10min obtains homogeneous transparent mixed liquor；
2) mixed liquor is added in the reaction kettle of 30mL polytetrafluoroethylliner liners, is put into baking oven, reaction is heated at 120 DEG C
24 hours, obtaining to bottom had the reaction solution that white precipitate is precipitated；
3) it will precipitate after being centrifuged with supernatant, with n,N-Dimethylformamide and ethyl alcohol respectively washing 2 times, finally freeze
It is dry, obtain nano metal organic framework material Uio-66-NH2；Resulting materials can emit stronger blue-fluorescence.
The modification preparation process of concealed fluorescent ink is as follows：
A ultrasonic disperse 15min in ethyl alcohol) is added in dry fluorescence NMOFs materials, and 0.5h is stirred at room temperature.
B ink solvent) is added, including:Ethylene glycol, glycerine, diethylene glycol (DEG) and surfactant SDS are ultrasonic again
15min, and room temperature quickly stirs 2h, can be obtained three primary colours fluorescent ink S@NMOFs.
In one of the embodiments, in step A) in, Eu-NMOFs powder is 20mg, and ethyl alcohol is 450 μ L；In step B)
In, ethylene glycol is 450 μ L, and glycerine is 50 μ L, and diethylene glycol (DEG) is 50 μ L, and surfactant SDS (3mg/mL) is 500 μ L.
In one of the embodiments, in step A) in, Tb-NMOFs powder is 10mg, and ethyl alcohol is 450 μ L；In step B)
In, ethylene glycol is 450 μ L, and glycerine is 50 μ L, and diethylene glycol (DEG) is 50 μ L, and surfactant SDS (3mg/mL) is 500 μ L.
In one of the embodiments, in step A) in, Uio-66-NH2Powder is 30mg, and ethyl alcohol is 450 μ L；In step
Rapid B) in, ethylene glycol is 450 μ L, and glycerine is 50 μ L, and diethylene glycol (DEG) is 50 μ L, and surfactant SDS (3mg/mL) is 500 μ L.
The design of novel invisible anti-fake two-dimension code is as follows：The color of lower fluorescence is excited to store list as signal using specific wavelength
The color of member, each encoding block fluorescence carries a coding information.One Quick Response Code is by different colours, same size, quantity
Adjustable hidden code block and the visible locating piece composition of three black.The two-dimension code image of printout is only shown under fluorescent light
Show three black locating pieces, but realizes decryption under the excitation of specific wavelength ultraviolet lamp, display and design tablet pattern identical two
Code information is tieed up, that is, has the function of multiple information encryption anti-counterfeiting.Since the color of fluorescence is that will have three bases by ink-jet printer
It is generated after the ink mixing of color fluorescent emission, therefore almost infinite more fluorescence color can be generated, realize infinite coding
Information.The size of coding information quantity can also be adjusted by the quantity of cell encoding block.To realize that this novel invisible is anti-
Pseudo- Quick Response Code, it is desirable that obtain the nanoscale fluorescent material of three primary colours to prepare ink；Three primary colours fluorescent ink passes through printer
It is printed after mixing, obtains the fluorescence of different colours；Three primary colours and its mixing chromatic ink not display color in the sunlight；Because passing through
Fluorescence realizes information storage and reading, so three primary colours and its secondary colour fluorescence must emit under single excitation.
Fig. 1 is the design diagram of novel invisible anti-fake two-dimension code, wherein：A is that transmitting red, green, blue three primary colours are glimmering respectively
The preparation process schematic diagram of the nanometer MOFs inks of light；B is ink-jet printer cartridge retrofit process schematic diagram；C is print procedure
Schematic diagram；D is printing false-proof information encryption and decryption processes schematic diagram.
Fig. 2 is the scanning electron microscope (SEM) photograph of the matrix group of the lanthanides nano metal organic framework materials of three primary colours ink, wherein：A is hair
Penetrate the Eu-NMOFs of red fluorescence；B is the Tb-NMOFs for emitting green fluorescence；C is the Dy-NMOFs for emitting blue-fluorescence；Illustration
For corresponding transmission electron microscope picture.The result shows that：The nano metal organic framework materials grain size and pattern of preparation are uniform, and size is about
200nm, the grain size be less than ink-jet print cartridge nozzle diameter 1/50, therefore will not plug nozzle, have be prepared into suitable spray
The potentiality of black marking ink.
Fig. 3 is the luminosity of the matrix group of the lanthanides nano metal organic framework materials of three primary colours ink, wherein：A is transmitting
Fluorescent emission figures of the Eu-NMOFs of red fluorescence under the excitation of 275nm wavelength；B is that the Tb-NMOFs of transmitting green fluorescence exists
Fluorescent emission figure under 275nm excitations；C is fluorescent emission figures of the Dy-NMOFs of transmitting blue-fluorescence under 275nm excitations；D
For position of the transmitting light color in cie color coordinate of three kinds of fluorescence MOFs.Illustrate in figure：Three kinds of obtained group of the lanthanides nanometers
Metal-organic framework material emits red, green, blue-fluorescence respectively, and spectrum is relatively narrow, and color is located at RGB in CIE
Area.
Fig. 4 is that three primary colours ink Eu-NMOFs, Tb-NMOFs and Dy-NMOFs press 1 respectively two-by-two:0、 1:2、1:1、2:1、
0:The luminescent spectrum and the coordinate position in CIE obtained after 1 volume ratio physical mixed, wherein：A is red fluorescence ink
Eu-NMOFs and the mixed luminescent spectrum figures of green fluorescence ink Tb-NMOFs；B is red fluorescence ink Eu-NMOFs and indigo plant
The mixed luminescent spectrum figures of color fluorescent ink Dy-NMOFs；C is green fluorescence ink Tb-NMOFs and blue-fluorescence ink Dy-
The mixed luminescent spectrum figures of NMOFs；D is coordinate position of the mixed luminescence spectrum in cie color.Illustrate in figure：It mixes two-by-two
The centre of fluorescence spectrum lucky position three primary colours fluorescence color coordinate in cie color coordinate of the ink transmitting of conjunction, entire ratio
The spectrum being mixed to get constitutes the triangle that a wider range covers a variety of colors in cie color coordinate, wherein red,
Green, blue three kinds emit three vertex for being located at triangle.
Fig. 5 is three primary colours ink Eu-NMOFs, Tb-NMOFs and Uio-66-NH2Press 1 respectively two-by-two:0,1:2,1:1,2:
1,0:The luminescent spectrum and the coordinate position figure in CIE obtained after 1 mixing, wherein：A is red fluorescence ink Eu-NMOFs
With the mixed luminescent spectrum figures of green fluorescence ink Tb-NMOFs；B is red fluorescence ink Eu-NMOFs and blue-fluorescence ink
The mixed luminescent spectrum figures of water Dy-NMOFs；C is green fluorescence ink Tb-NMOFs and blue-fluorescence ink Dy-NMOFs mixed
Luminescent spectrum figure after conjunction；D is coordinate of the mixed luminescence spectrum in CIE.Illustrate in figure：Uio66-NH2With Dy-NMOFs phases
Than the blue-fluorescence intensity higher emitted under 275nm excitations is in deeper blue region in cie color coordinate, therefore obtains
Better mixing fluorescence color is arrived.As a result while also illustrating, fluorescent ink material, which is not limited to lanthanide series metal nano metal, to be had
Machine frame frame material, other meet particle size, excitation wavelength and transmitting position and can be used in the technology.
Fig. 6 is that red fluorescence ink Eu-NMOFs and green fluorescence ink Tb-NMOFs presses 1 respectively:0,0:1, 1:1,1:
1.001,1:1.01,1:1.1,1:2,1:1.3,1:1.4 and 1:1.5 mixed luminescent spectrums and the coordinate position in CIE.
Illustrate in figure：In the case where the difference of mixed proportion is smaller, mixed spectrum is more similar, only has in intensity small
Difference, although the more difficult differentiation of naked eyes, the position in cie color coordinate is different.
Table 1 is that red fluorescence ink Eu-NMOFs and green fluorescence ink Tb-NMOFs presses 1 respectively:0,0:1, 1:1,1:
1.001,1:1.01,1:1.1,1:2,1:1.3,1:1.4 and 1:Coordinate position of the 1.5 mixed luminescence spectrum in CIE.It is said in table
It is bright：Even if coordinate value area of the spectrum in CIE chromaticity diagram can be passed through if when the volume difference when ink mixes only has 0.001
Point, the differentiation precision of △ x=0.0002, △ y=0.0006 can be reached.To the good discrimination ability of this kind of close fluorescence color
It illustrates using fluorescence color as the feasibility of signal identification unit progress information coding, while also illustrating the antifalse Quick Response Code
Coding strategy possesses huge information capacity to realize safer encryption function.
Table 1
Fig. 7 is the writing effect figure of the pen core made of three primary colours ink, wherein：A, B is respectively by Eu-NMOFs, Tb-
NMOFs and Uio-66-NH2Ink is mounted in the photo of manufactured water-color paintbrush under fluorescent light and in the UV lamp in pen core；C, D is point
It Yong not red fluorescence ink Eu-NMOFs, green fluorescence ink Tb-NMOFs, blue-fluorescence ink Uio-66-NH2It writes
The acronym " N " of " Nankai University ", " K ", " U " respectively under fluorescent light with the photo under ultraviolet lamp；E is C
The surface topography of circled under a scanning electron microscope in figure, the particle of high-visible complete nanometer MOFs.Illustrate in figure：
After being prepared into ink, the luminosity of such luminescent material is effectively maintained；By writing impression and scanning electron microscope (SEM) photograph
Piece can be seen that the ink has excellent fluid property and grain size stability.
Fig. 8 A-C be design input two-dimension code pattern, the Quick Response Code of printing under fluorescent light and 275nm ultraviolet lamp
Under photo；Fig. 8 D be design with fluorescence color and position be identify item bar code fluorescent lamp and ultraviolet lamp excitation under
Photo.Fig. 8 E are that the heart of design and the superposed graph of crescent moon are printed upon on RMB, respectively under fluorescent lamp and ultraviolet lamp
Recruitment.Illustrate in figure：The two-dimension code image of inkjet printing output only shows three darkened locations blocks under common light, specific
The lower display of 275nm ultraviolet lamps excitation Quick Response Code coding information identical with the figure inputted, that is, it is anti-fake to realize novel invisible
Quick Response Code coding techniques.Meanwhile the size and number of information unit colour block in Quick Response Code is inputted by design, two dimension is adjusted
The information capacity of code.In addition, prepared concealed fluorescent ink can be additionally used in concealed anti-false pattern label.
Claims (10)
1. a kind of novel invisible anti-fake two-dimension code based on nano metal organic framework materials, it is characterized in that：The novel invisible is anti-
Pseudo- Quick Response Code by transmitting red, green and blue fluorescence nano metal organic framework materials be printed as different coding squares and
The ratio of three vertex black locating piece compositions, three kinds of different fluorescence color inks decides square under specific wavelength excitation
The fluorescence color of fluorescence color, different coding square as information memory cell and carries coding information.
2. the novel invisible anti-fake two-dimension code according to claim 1 based on nano metal organic framework materials, feature
It is：Using fluorescence color and arrangement as information memory cell, it is different from arranging as information unit using square size and black and white
QD codes, also different from using line width and gap size as the bar code of information unit.
3. the novel invisible anti-fake two-dimension code according to claim 1 based on nano metal organic framework materials, feature
It is：By transmitting, the three primary colours fluorescent ink of red, green and blue fluorescence nano metal organic framework materials prints for it,
The ratio of three kinds of different fluorescence color inks decides the fluorescence color of different coding block.Three primary colours and its secondary colour fluorescence are same
The light excitation of one wavelength is lower to be generated.
4. the novel invisible anti-fake two-dimension code according to claim 3 based on nano metal organic framework materials, feature
It is：The preparation process of the three primary colours fluorescent ink is as follows：
1) by anhydrous group of the lanthanides chloride, 1,3- terephthalic acid (TPA), 3,5- dicarboxyl phenyl boric acids are added to n,N-Dimethylformamide
In water, ultrasonic dissolution 10min obtains homogeneous transparent mixed liquor；
2) mixed liquor is added in polytetrafluoroethylliner liner and is inserted in reaction kettle, be put into baking oven, reaction is heated at 120 DEG C
6 hours, obtaining to bottom had the reaction solution that white precipitate is precipitated；
3) precipitation is centrifuged with supernatant, n,N-Dimethylformamide and ethyl alcohol is used in combination, and respectively washing 2 times, finally drying are
The metal-organic framework materials Ln-NMOFs of the about 200nm of red, green, blue color fluorescence can be emitted respectively；
4) by ZrCl4, amino terephthalic acid (TPA) and benzoic acid be added in n,N-Dimethylformamide and a small amount of hydrochloric acid, ultrasound is molten
10min is solved, homogeneous transparent mixed liquor is obtained；
5) mixed liquor is added in polytetrafluoroethylliner liner and is inserted in reaction kettle, be put into baking oven, reaction is heated at 120 DEG C
48 hours, obtaining to bottom had the reaction solution that white precipitate is precipitated；
6) precipitation is centrifuged with supernatant, n,N-Dimethylformamide and ethyl alcohol is used in combination, and respectively washing 2 times, finally drying are
It can obtain the Uio-66-NH of the stronger blue-fluorescence of transmitting of about 90nm2；
7) ultrasonic disperse 15min in ethyl alcohol is added in dry fluorescence NMOFs materials, and 0.5h is stirred at room temperature；
8) mixed solvent, ethylene glycol, glycerine, diethylene glycol (DEG) and surfactant SDS ultrasound 15min, and room temperature again is added
Quickly stirring 2h is emitted red, green, blue color fluorescent ink S@NMOFs respectively.
5. the novel invisible anti-fake two-dimension code according to claim 4 based on nano metal organic framework materials, feature
It is：Three kinds of group of the lanthanides Ln-MOFs synthetic methods are characterized in：
The anhydrous group of the lanthanides chloride is Europium chloride, obtains Eu-NMOFs, and red is shown under the laser irradiation of 275nm wavelength
Fluorescence；
The anhydrous group of the lanthanides chloride is terbium chloride, obtains Tb-NMOFs, and green is shown under the laser irradiation of 275nm wavelength
Fluorescence；
The anhydrous group of the lanthanides chloride is dysprosium chloride, obtains Dy-NMOFs, and blue is shown under the laser irradiation of 275nm wavelength
Fluorescence.
6. the novel invisible anti-fake two-dimension code according to claim 4 based on nano metal organic framework materials, feature
It is：Anhydrous group of the lanthanides chloride, 1,3- terephthalic acid (TPA)s, 3,5- dicarboxyls phenyl boric acid and N,N-dimethylformamide in step 1),
The amount ratio of water is 0.02mmol:0.01mmol:0.01mmol:7mL:3mL.
7. the novel invisible anti-fake two-dimension code according to claim 4 based on nano metal organic framework materials, feature
It is：ZrCl in step 4)4, amino terephthalic acid (TPA), benzoic acid, N,N-dimethylformamide and hydrochloric acid amount ratio be:
0.33mmol:0.26mmol:5mmol:6mL:55μL。
8. the novel invisible anti-fake two-dimension code according to claim 4 based on nano metal organic framework materials, feature
It is：Step 7) and 8) in ethyl alcohol, ethylene glycol, glycerine, diethylene glycol (DEG), surfactant SDS amount ratio be：450μL:450μL:
50μL:50μL:500μL。
9. the novel invisible anti-fake two-dimension code according to claim 4 based on nano metal organic framework materials, feature
It is：The purpose of synthesis of Ln-NMOFs is to obtain three kinds under single wavelength excitation, and transmitting is red, green and blue fluorescence respectively
Ln-NMOFs, other can emit red, green and blue fluorescence fluorescent illuminant under same excitation wavelength, it can also be used to
Realize the novel invisible fluorescence falsification preventing Quick Response Code.
10. the application of the fluorescent ink S@NMOFs prepared by claim 4 a kind of, it is characterised in that：By the way that the ink is perfused
The print cartridge of ink-jet printer is designed using fluorescence color as the anti-fake two-dimension code of signal identification unit, is obtained in fluorescent lamp after printing
The black block of lower display positioning, the anti-fake two dimension of the novel invisible of code displaying information under the ultraviolet lamp of specific wavelength 275nm
Code.
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